Advertisement

Journal of Applied Electrochemistry

, Volume 49, Issue 5, pp 503–515 | Cite as

Capacitive properties, structure, and composition of porous Co hydroxide/oxide layers formed by dealloying of Zn–Co alloy

  • Svetlana Lichušina
  • Laurynas Staišiūnas
  • Vitalija Jasulaitienė
  • Algirdas Selskis
  • Konstantinas LeinartasEmail author
Research Article
  • 66 Downloads
Part of the following topical collections:
  1. Capacitors

Abstract

Thin porous binder-free layers of Co hydroxide/oxide for electrochemical capacitors were formed by dealloying an electrochemically deposited binary Zn–Co alloy, consisting of single homogeneous γ-Zn21Co5 phase. Scanning electron microscopy with energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy (XPS) was used to assess the structure, thickness, and distribution of elements in the as-deposited alloy and the dealloyed layers. The most developed porous layers were formed at a dealloying potential of − 0.965 V versus Ag/AgCl. Both the as-deposited Zn–Co and the dealloyed layers were characterized by a relatively uniform distribution of the components. As determined by XPS, the top of the dealloyed layers before cycling consisted of Co(II) hydroxide with traces of Co(0) and Co(III). The capacitive properties and stability of the formed layers of porous Co oxides were assessed using the electrochemical cyclic voltammetry (CV) and the constant current charge–discharge (C–D) methods. The areal and volumetric pseudo-capacitance values of ~ 0.38 F cm−2 and ~ 880 F cm−3, respectively, were calculated for a 4.3-µm-thick layer. The stability of the studied Co hydroxide/oxides layers was evaluated by CV and C–D cycling. After 300 cycles of C–D, the retention of pseudo-capacitance ~ 80% and the Coulombic efficiency of ~ 98% were determined. The long-term pseudo-capacitance retention was estimated at ~ 78.3% of the initial value.

Graphical abstract

Keywords

Zinc cobalt alloy Electrochemical dealloying Cobalt hydroxides/oxides Pseudo-capacitance 

Notes

Acknowledgements

The assistance of S. Stanionytė in XRD measurements of the deposited and the dealloyed Zn–Co layers is greatly acknowledged. This research did not receive any specific grant from funding agencies in the public, commercial, or not-for-profit sectors.

References

  1. 1.
    Snyder J, Fujita T, Chen MW, Erlebacher J (2010) Oxygen reduction in nanoporous metal–ionic liquid composite electrocatalysts. Nat Mater 9:904–9072CrossRefGoogle Scholar
  2. 2.
    Wittstock A, Zielasek V, Biener J, Friend CM, Baumer M (2010) Nanoporous gold catalysts for selective gas-phase oxidative coupling of methanol at low temperature. Science 327:319–322CrossRefGoogle Scholar
  3. 3.
    Qiu H, Xue L, Ji G, Zhou G, Huang X, Qu Y, Gao P (2009) Enzyme-modified nanoporous gold-based electrochemical biosensors. Biosens Bioelectron 24:3014–3018CrossRefGoogle Scholar
  4. 4.
    Biener J, Wittstock A, Zepeda-Ruiz LA, Biener MM, Zielasek V, Kramer D, Viswanath RN, Weissmuller J, Baumer M, Hamza AV (2009) Surface-chemistry-driven actuation in nanoporous gold. Nat Mater 8:47–51CrossRefGoogle Scholar
  5. 5.
    Ding Y, Chen MW (2009) Nanoporous metals for catalytic and optical applications. MRS Bull 34:569–576CrossRefGoogle Scholar
  6. 6.
    Le Comte A, Brousse T, Belanger D (2016) New generation of hybrid carbon/Ni(OH)2 electrochemical capacitor using functionalized carbon electrode. J Power Sources 326:702–710CrossRefGoogle Scholar
  7. 7.
    Lang X, Hirata A, Fujita T, Chen M (2011) Nanoporous metal/oxide hybrid electrodes for electrochemical supercapacitors. Nat Nanotechnol 6:232–236CrossRefGoogle Scholar
  8. 8.
    Nwanya AC, Obi D, Osuji RU, Bucher R, Maaza M, Ezema FI (2017) Simple chemical route for nanorod-like cobalt oxide films for electrochemical energy storage applications. J Solid State Electrochem 21:2567–2576CrossRefGoogle Scholar
  9. 9.
    Okman O, Lee D, Kysar JW (2010) Fabrication of crack-free nanoporous gold blanket thin films by potentiostatic dealloying. Scr Mater 63:1005–1008CrossRefGoogle Scholar
  10. 10.
    Senior NA, Newman RC (2006) Synthesis of tough nanoporous metals by controlled electrolytic dealloying. Nanotechnology 17:2311–2316CrossRefGoogle Scholar
  11. 11.
    Hakamada M, Mabuchi M (2009) Preparation of nanoporous palladium by dealloying: anodic polarization behaviors of Pd-M (M = Fe, Co, Ni) alloys. Mater Trans JIM 50:431–435CrossRefGoogle Scholar
  12. 12.
    Erlebacher J (2004) An atomistic description of dealloying: porosity evolution, the critical potential, and rate-limiting behavior. J Electrochem Soc 151:C614–C626CrossRefGoogle Scholar
  13. 13.
    Forty AJ (1979) Corrosion micromorphology of noble metal alloys and depletion gilding. Nature 282:597–598CrossRefGoogle Scholar
  14. 14.
    Sieradzki K (1993) Curvature effects in alloy dissolution. J Electrochem Soc 140:2868–2872CrossRefGoogle Scholar
  15. 15.
    Erlebacher J, Aziz MJ, Karma A, Dimitrov N, Sieradzki K (2001) Evolution of nanoporosity in dealloying. Nature 410:450–453CrossRefGoogle Scholar
  16. 16.
    Zinchenko O, De Raedt HA, Detsi E, Onck PR, De Hosson JTM (2013) Nanoporous gold formation by dealloying: a metropolis Monte Carlo study. Comput Phys Commun 184:1562–1569CrossRefGoogle Scholar
  17. 17.
    Zhao F, Zeng J, Santos GM, Shih W-Ch (2015) In situ pattering of hierarchical nanoporous gold structures by in-plane dealloying. Mater Sci Eng B 194:34–40CrossRefGoogle Scholar
  18. 18.
    Jia F, Yu Ch, Deng K, Zhang L (2007) Nanoporous metal (Cu, Ag, Au) films with high surface area: General fabrication and preliminary electrochemical performance. J Phys Chem C 111:8424–8431CrossRefGoogle Scholar
  19. 19.
    Wang Y, Wang Y, Ji H, Yan X, Gao H, Ma W, Zhang Zh (2016) Microstructural and compositional evolution of nanoporous silver during dealloying of rapidly solidified Mg65Ag35 alloy. Intermetallics 76:49–55CrossRefGoogle Scholar
  20. 20.
    Chen LY, Guo H, Fujita T, Hirata A, Zhang W, Inoue A, Chen MW (2011) Nanoporous PdNi bimetallic catalyst with enhanced electrocatalytic performances for electro-oxidation and oxygen reduction reactions. Adv Funct Mater 21:4364–4370CrossRefGoogle Scholar
  21. 21.
    Stratmann M, Rohwerder M (2001) Materials science: a pore view of corrosion. Nature 410:420–423CrossRefGoogle Scholar
  22. 22.
    Erlebacher J, Seshadri R (2009) Hard materials with tunable porosity. MRS Bull 34:561–566CrossRefGoogle Scholar
  23. 23.
    Snyder J, Asanithi P, Dalton AB, Erlebacher J (2008) Stabilized nanoporous metals by dealloying ternary alloy precursors. Adv Mater 20:4883 4886CrossRefGoogle Scholar
  24. 24.
    Yamauchi I, Kawamura H, Nakano K, Tanaka T (2005) Formation of fine skeletal Co–Ag by chemical leaching of Al–Co–Ag ternary alloys. J Alloys Compd 387:187–192CrossRefGoogle Scholar
  25. 25.
    Qiu HJ, Wang JQ, Liu P, Wang Y, Chen MW (2015) Hierarchical nanoporous metal/metal-oxide composite by dealloying metallic glass for high-performance energy storage. Corros Sci 96:196–202CrossRefGoogle Scholar
  26. 26.
    Rizzi P, Scaglione F, Battezzati L (2014) Nanoporous gold by dealloying of an amorphous precursor. J Alloys Compd 586:S117–S120CrossRefGoogle Scholar
  27. 27.
    Wada T, Geslin P-A, Kato H (2018) Preparation of hierarchical porous metals by two-step liquid metal dealloying. Scr Mater 142:101–105CrossRefGoogle Scholar
  28. 28.
    Song T, Yan M, Shi Z, Atrens A, Qian M (2015) Creation of bimodal porous copper materials by an annealing-electrochemical dealloying approach. Electrochim Acta 164:288–296CrossRefGoogle Scholar
  29. 29.
    Tuan NT, Park J, Lee J, Gwak J, Lee D (2014) Synthesis of nanoporous Cu films by dealloying of electrochemically deposited Cu–Zn alloy films. Corros Sci 80:7–11CrossRefGoogle Scholar
  30. 30.
    Lu H-B, Li Y, Wang F-H (2007) Synthesis of porous copper from nanocrystalline two-phase Cu–Zr film by dealloying. Scr Mater 56:165–168CrossRefGoogle Scholar
  31. 31.
    Hayes JR, Hodge AM, Biener J, Hamza AV, Sieradzki K (2006) Monolithic nanoporous copper by dealloying Mn–Cu. J Mater Res 21:2611–2616CrossRefGoogle Scholar
  32. 32.
    Liu W, Chen L, Yan J, Li N, Shi S, Zhang Sh (2015) Dealloying solution dependence of fabrication, microstructure and porosity of hierarchical structured nanoporous copper ribbons. Corros Sci 94:114–121CrossRefGoogle Scholar
  33. 33.
    Pryor MJ, Fister JC (1984) The mechanism of dealloying of copper solid solutions and intermetallic phases. J Electrochem Soc 131:1230–1235CrossRefGoogle Scholar
  34. 34.
    Qiu H-J, Kang JL, Liu P, Hirata A, Fujita T, Chen MW (2014) Fabrication of large-scale nanoporous nickel with a tunable pore size for energy storage. J Power Sources 247:896–905CrossRefGoogle Scholar
  35. 35.
    Qiu H-J, Ito Y, Chen MW (2014) Hierarchical nanoporous nickel alloy as three-dimensional electrodes for high-efficiency energy storage. Scr Mater 89:69–72CrossRefGoogle Scholar
  36. 36.
    Hakamada M, Mabuchi M (2009) Preparation of nanoporous Ni and Ni–Cu by dealloying of rolled Ni–Mn and Ni–Cu–Mn alloys. J Alloys Compd 485:583–587CrossRefGoogle Scholar
  37. 37.
    Stein M, Owens SP, Pickering HW, Weil KG (1998) Dealloying studies with electrodeposited zinc-nickel alloy films. Electrochim Acta 43:223–226CrossRefGoogle Scholar
  38. 38.
    Gobal F, Faraji M (2013) Fabrication of nanoporous nickel oxide by de-zincification of Zn–Ni/(TiO2-nanotubes) for use in electrochemical supercapacitors. Electrochim Acta 100:133–139CrossRefGoogle Scholar
  39. 39.
    Nwanya AC, Obi D, Osuji RU, Bucher R, Maaza M (2017) Simple chemical route for nanorod-like cobalt oxide films for electrochemical energy storage applications. J Solid State Electrochem 21:2567–2576CrossRefGoogle Scholar
  40. 40.
    Jagadale AD, Kumbhar VS, Lokhande CD (2013) Supercapacitive activities of potentiodynamically deposited nanoflakes of cobalt oxide (Co3O4) thin film electrode. J Colloid Interface Sci 406:225–230CrossRefGoogle Scholar
  41. 41.
    Jagadale AD, Kumbhar VS, Bulakhe RN, Lokhande CD (2014) Influence of electrodeposition modes on the supercapacitive performance of Co3O4 electrodes. Energy 64:234–241CrossRefGoogle Scholar
  42. 42.
    Kandalkar SG, Dhawale DS, Kim C-K, Lokhande CD (2010) Chemical synthesis of cobalt oxide thin film electrode for supercapacitor application. Synth Met 160:1299–1302CrossRefGoogle Scholar
  43. 43.
    Yan J, Wei T, Qiao W, Shao B, Zhao Q, Zhang L, Fan Z (2010) Rapid microwave-assisted synthesis of graphene nanosheet/Co3O4 composite for supercapacitors. Electrochim Acta 55:6973–6978CrossRefGoogle Scholar
  44. 44.
    Kumar M, Subramania A, Balakrishnan K (2014) Preparation of electrospun Co3O4 nanofibers as electrode material for high performance asymmetric supercapacitors. Electrochim Acta 149:152–158CrossRefGoogle Scholar
  45. 45.
    Feng C, Zhang J, Deng Y, Zhong C, Liu L, Hu W (2015) One-pot fabrication of Co3O4 microspheres via hydrothermal method at low temperature for high capacity supercapacitor. Mater Sci Eng B 199:15–21CrossRefGoogle Scholar
  46. 46.
    Vlamidis Y, Scavetta E, Giorgetti M, Sangiorgi N, Tonelli D (2017) Electrochemically synthesized cobalt redox active layered double hydroxides for supercapacitors development. Appl Clay Sci 143:151–158CrossRefGoogle Scholar
  47. 47.
    Li G, Song X, Sun Z, Yang S, Ding B, Yang S, Yang Zh, Wang F (2011) Nanoporous Ag prepared from the melt-spun Cu-Ag alloys. Solid State Sci 13:1379 1384Google Scholar
  48. 48.
    Wang X, Qi Z, Zhao C, Wang W, Zhang Z (2009) Influence of alloy composition and dealloying solution on the formation and microstructure of monolithic nanoporous silver through chemical dealloying of Al–Ag alloys. J Phys Chem C 113:13139–13150CrossRefGoogle Scholar
  49. 49.
    Scaglione F, Gebert A, Battezzati L (2010) Dealloying of an Au-based amorphous alloy. Intermetallics 18:2338–2342CrossRefGoogle Scholar
  50. 50.
    Li H, Zhu M, Pang Y, Du H, Liu T (2016) Influences of ultrasonic irradiation on the morphology and structure of nanoporous Co nanoparticles during chemical dealloying. Prog Nat Sci Mater 26:562–566CrossRefGoogle Scholar
  51. 51.
    Wang Z, Fei P, Xiong H, Qin Ch, Zhao W, Liu X (2017) CoFe2O4 nanoplates synthesized by dealloying method as high performance Li-ion battery anodes. Electrochim Acta 252:295–305CrossRefGoogle Scholar
  52. 52.
    Liu H, Wang X, Wang J, Xu H, Yu W, Dong X, Zhang H, Wang L (2017) Hierarchical porous CoNi/CoO/NiO composites derived from dealloyed quasicrystals as advanced anodes for lithium-ion batteries. Scripta Mater 139:30–33CrossRefGoogle Scholar
  53. 53.
    Juzeliūnas E, Lichušina S Patent of the Republic of Lithuania No. 5481 26.03.2008Google Scholar
  54. 54.
    Wagner CD, Naumkin AV, Kraut-Vass A, Allison JW, Powell CJ, Rumble JRJr (2003) NIST standard reference database 20, Version 3.4 (web version) http://srdata.nist.gov/xps/
  55. 55.
    Lichušina S, Sudavičius A, Juškėnas R, Bučinskienė D, Juzeliūnas E (2008) Deposition of Co rich Zn-Co alloy coatings of high corrosion resistance. Trans IMF 86:141–147CrossRefGoogle Scholar
  56. 56.
    Smith AJ, Trimm DL (2005) The preparation of skeletal catalysts. Annu Rev Mater Res 35:127–142CrossRefGoogle Scholar
  57. 57.
    Lichušina S, Chodosovskaja A, Selskis A, Leinartas K, Miečinskas P, Juzeliūnas E (2008) Pseudocapacitive behaviour of cobalt oxide films on nano-fibre and magnetron sputtered substrates. Chemija 19:6–14Google Scholar
  58. 58.
    Mokaddem M, Volovitch P, Ogle K (2010) The anodic dissolution of zinc and zinc alloys in alkaline solution. I. Oxide formation on electrogalvanized steel. Electrochim Acta 55:7867–7875CrossRefGoogle Scholar
  59. 59.
    Barbero C, Planes GA, Miras MC (2001) Redox coupled ion exchange in cobalt oxide films. Electrochem Comm 3:113–116CrossRefGoogle Scholar
  60. 60.
    Liang Y-Y, Bao Sh -J, Li H-L (2007) Nanocrystalline nickel cobalt hydroxides/ultrastable Y zeolite composite for electrochemical capacitors. J Solid State Electrochem 11:571–576CrossRefGoogle Scholar
  61. 61.
    Gupta V, Gupta S, Miura N (2009) Electrochemically synthesized large area network of CoxNiyAlz layered triple hydroxides nanosheets: a high performance supercapacitor. J Power Sources 189:1292–1295CrossRefGoogle Scholar
  62. 62.
    Liu N, Li J, Ma W, Liu W, Shi Y, Tao J, Zhang X, Su J, Li L, Gao Y (2014) Ultrathin and lightweight 3D free-standing Ni@NiO nanowire membrane electrode for a supercapacitor with excellent capacitance retention at high rates. ACS Appl Mater Interfaces 6:13627–13634CrossRefGoogle Scholar
  63. 63.
    Fischer AE, Saunders MP, Pettigrew KA, Rolison DR, Long JW (2008) Electroless deposition of nanoscale MnO2 on ultraporous carbon nanoarchitectures: correlation of evolving pore-solid structure and electrochemical performance. J Electrochem Soc 155:A246–A252CrossRefGoogle Scholar
  64. 64.
    Yang J, Liu H, Martens WN, Frost RL (2010) Synthesis and characterization of cobalt hydroxide, cobalt oxyhydroxide and cobalt oxide nanodiscs. J Phys Chem C 114:111–119CrossRefGoogle Scholar
  65. 65.
    Galtayries A, Grimblot J (1999) Formation and electronic properties of oxide and sulphide films of Co, Ni and Mo studied by XPS. J Electron Spectrosc Relat Phenom 98–99:267–275CrossRefGoogle Scholar
  66. 66.
    Biesinger MC, Payne BP, Grosvenor AP, Lau LWM, Gerson AR, Smart RSC (2011) Resolving surface chemical states in XPS analysis of first row transition metals, oxides and hydroxides: Cr, Mn, Fe, Co and Ni. Appl Surf Sci 257:2717–2730CrossRefGoogle Scholar
  67. 67.
    Hu C-C, Liu M-J, Chang K-H (2007) Anodic deposition of hydrous ruthenium oxide for supercapacitors. J Power Sources 163:1126–1131CrossRefGoogle Scholar
  68. 68.
    Da Silva LM, Boodts JFC, DeFaria LA (2000) ‘In situ’ and ‘ex situ’ characterization of the surface properties of the RuO2 (x) + Co3O4 (1 – x) system. Electrochim Acta 45:2719–2727CrossRefGoogle Scholar
  69. 69.
    Hu C-C, Chen W-C, Chang K-H (2004) How to achieve maximum utilization of hydrous ruthenium oxide for supercapacitors. J Electrochem Soc 151:A281–A290CrossRefGoogle Scholar

Copyright information

© Springer Nature B.V. 2019

Authors and Affiliations

  1. 1.Center for Physical Sciences and TechnologyVilniusLithuania

Personalised recommendations